EP0733672B1 - Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité - Google Patents

Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité Download PDF

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Publication number
EP0733672B1
EP0733672B1 EP95104158A EP95104158A EP0733672B1 EP 0733672 B1 EP0733672 B1 EP 0733672B1 EP 95104158 A EP95104158 A EP 95104158A EP 95104158 A EP95104158 A EP 95104158A EP 0733672 B1 EP0733672 B1 EP 0733672B1
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EP
European Patent Office
Prior art keywords
silicone
process according
component
components
mixing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95104158A
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German (de)
English (en)
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EP0733672A1 (fr
Inventor
Heinz Westhoff
Franz-Josef Giesen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sonderhoff Chemicals GmbH
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Sonderhoff Chemicals GmbH
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Publication date
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Priority to DE59500604T priority Critical patent/DE59500604D1/de
Priority to EP95104158A priority patent/EP0733672B1/fr
Priority to AT95104158T priority patent/ATE157685T1/de
Publication of EP0733672A1 publication Critical patent/EP0733672A1/fr
Application granted granted Critical
Publication of EP0733672B1 publication Critical patent/EP0733672B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Definitions

  • the invention relates to a method for producing a foamed or non-foamed soft-elastic silicone elastomer, in particular for sealing purposes, especially for housing and cover seals, using a two-component, addition-crosslinking silicone system in accordance with the type specified in the preamble of claim 1.
  • a method of this type, to which the invention preferably relates, is known from EP 0 416 229 B1.
  • the two-component silicone system is processed using a low-pressure two-component mixing and dosing system. It has been shown that this processing technique, which can be mastered well from a procedural point of view, makes it possible to produce extremely high-quality silicone foam seals without the addition of heat, that is to say at ambient temperature, if on the one hand the addition of water as a blowing agent to the reaction mixture is at most 2% by weight, based on the amount Silicone polymer, is limited and if, on the other hand, the specific reaction mixture consisting of the two components is processed by means of a low-pressure two-component mixing and metering system, the mixing head of which has a rod-shaped mixing element rotating at high speed in a narrow mixing channel, the speed of rotation of the mixing element being 3000 up to 8000 rpm.
  • the mixing channel leading axially through the mixing head is set in cross-section such that the passage gap between the channel wall and the mixing element rotating axially in the mixing channel is extremely narrow, ie 0.5 to 3 mm.
  • the high-quality silicone foams produced by this procedure are considerably more expensive than the conventional polyurethane foams, so that there are limits to their use.
  • polyurethane foams have a permanently elastic behavior up to a temperature of + 90 ° C.
  • Silicone foams are superior to polyurethane foams in terms of temperature and chemical resistance. Their temperature resistance is on the order of 200 to 300 ° C. However, the silicone foams have a price 5 times higher than the polyurethane foams used for sealing purposes.
  • the high temperature resistance of the silicones is used in many areas of application in which the silicones are thermally stressed in use, e.g. in motor vehicles in the automotive industry, not fully exhausted.
  • the preferred temperature range is generally 100 to 150 ° C, a temperature range that excludes the use of the much cheaper polyurethane foam seals.
  • hollow microspheres consist of expanded, microfine polymer hollow spheres which are provided with an inert covering, ie a covering made of an inorganic mineral substance, which is required for their production.
  • inert covering ie a covering made of an inorganic mineral substance, which is required for their production.
  • These fillers are available on the market under the name "Duralite M” (company Omya GmbH, Cologne). So far, these fillers have not been considered for the use of these fillers consisting of micro-hollow spheres in silicones, which are known to have special requirements with regard to the fatigue strength, the elasticity behavior required especially for seals and mostly also the temperature resistance.
  • the polymer hollow spheres at about 120 ° to 150 ° C have only a limited temperature resistance, which is significantly below that of the silicones, and that the hollow micro spheres are also coated with calcium carbonate, i.e. a hygroscopic mineral that softens, becomes sticky and lubricates in a water atmosphere and therefore appears to be unusable for silicone processing technology.
  • calcium carbonate i.e. a hygroscopic mineral that softens, becomes sticky and lubricates in a water atmosphere and therefore appears to be unusable for silicone processing technology.
  • these fillers which consist of hollow microspheres, can also be used successfully in the production of silicone products if they are produced using a two-component mixing and metering system and addition-crosslinking silicones. It was found that the silicone materials obtained, whether in the form of non-foamed or foamed silicone elastomers are not significantly adversely affected by the addition of these specific fillers with regard to their mechanical strength properties and also with regard to their elasticity and pressure behavior, which are indispensable for their suitability as sealants, although the density of the silicone mass is greatly reduced by the addition of these fillers.
  • the method according to the invention can advantageously be carried out in the manner disclosed in EP 0 416 229 B1, to which reference is made here.
  • hollow microspheres those made from a polyacrylonitrile copolymer or from a polyvinylidene chloride copolymer are primarily used.
  • the known hollow microspheres have a mineral coating made of calcium carbonate.
  • hollow microspheres with a different inorganic, mineral coating can also be used in the process according to the invention, e.g. with one of talc, silica or the like.
  • water is additionally added as a blowing agent to the component (A) comprising the silicone polymer and the platinum catalyst to produce a silicone foam or a silicone sealing foam, preferably in an amount of at most 2% by weight, based on the total amount of silicone polymer in the silicone system.
  • the two components of the silicone system are set so that they can be processed in a mixing ratio of 1: 1 on the two-component mixing and dosing system, which is particularly important in terms of the safety of the process and also in relation to the exact quantity metering of the components brings considerable advantages.
  • Each of the two components has a proportion of silicone polymer with at least two vinyl groups in the molecule and, as filler and extender, the hollow microspheres mentioned, preferably in equal amounts.
  • the silicone system can be cured without the addition of heat, that is to say at normal room temperatures, generally also in situ.
  • a reaction mixture of the two components is processed without water as a blowing agent and without an excess of hydrogen siloxane.
  • the silicone system consisting of the two components can also be processed for mold foaming with the aid of a known high-pressure two-component mixing and metering system.
  • an organic platinum catalyst is used in a further development of the process according to the invention which, based on 1000 g of the silicone polymer contained in the reaction mass, contains between 300 and 3000 ppm, preferably 300 to 900 ppm, of platinum.
  • a polyhydrogensiloxane with an SiH content of 15 mmol / g is expediently used here as the hydrogen siloxane.
  • the two-component, addition-crosslinking silicone system has a special catalysis system, preferably in combination with a special crosslinker system. While in the conventional processes, platinum catalysts with a platinum content of mostly only 30 ppm per kg of silicone polymer are used, the stated process uses a 10 to 100 times larger dosage of the platinum content.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the silicone foam obtained fulfills the requirements imposed on the usual silicone sealing compounds, the density of which is 0.45 g / ccm, but has a foam density reduced by a factor of about 3.
  • the saving in terms of material costs compared to the usual silicone sealants has a factor of 3.
  • silicone foams with foam densities of about 0.07 g / ccm are obtained in the above-mentioned recipe at processing temperatures of 25 to 30 ° C .
  • These silicone foams are particularly well suited for molded foams and can be used, for example, as molded foams in aircraft seats or in the form of molded plates as heat shields, as are required above all in motor vehicle construction as protection against heat radiation from the engine.
  • the silicone system specified in Example 1 can also be used for mold foaming, where it is processed using a high-pressure two-component mixing and metering system.
  • the silicone system according to Example 1 contains no water as a blowing agent and also no excess of hydrogen siloxane, then it can be used to produce a low-density, non-foamed elastic silicone elastomer, which is also suitable for sealing purposes.
  • the silicone system according to Example 1 is modified so that it uses an organic platinum catalyst which, based on 1000 g of the silicone polymer contained in the reaction mass, contains between 300 and 900 ppm of platinum, a polyhydrogensiloxane with an SiH content of 15 mmol / g is used. This creates a silicone foam with a high resilience, which is also ideal for sealing purposes.
  • the silicone elastomer obtained or the product made from it is subjected to an annealing process over a period of 15 to 20 minutes. subjected to a temperature of 120 ° C to 200 ° C to split off the residual hydrogen and thus suppress the post-crosslinking.
  • both components A and B are added as fillers and extenders to the mineral-coated elastic hollow microspheres mentioned, in each case in proportions of 2 to 20% by weight, preferably 6 to 15% by weight, based on the Proportion of silicon polymer in the component in question.
  • the coated hollow microspheres have a density of 0.05 to 0.15 g / ccm. They are sufficiently shear-resistant for processing and can even be used as gear pumps with gear pumps. Gear pumps have the advantage over piston and peristaltic pumps of a very precise dosage, which is particularly important for a uniform sealing quality of the silicone sealing foam.
  • foamed or also non-foamed silicone products can be produced in a processing-technically simple manner, which are particularly well suited for sealing purposes, in particular also for seals that are thermally loaded up to about 200 ° C.
  • Main areas of application for the silicone sealants produced according to the invention are housing and cover seals, seals in automobile construction and in appliance construction, in principle with advantage wherever polyurethane foams can no longer be used due to their temperature resistance limited to approx. 90 ° C and / or the other good properties of the Silicone compounds, especially their chemical resistance, are required.
  • silicone reaction masses obtained by mixing the two components A and B are cured without the addition of heat, i.e. at normal ambient temperatures and preferably in situ, i.e. with seals on the seat thereof, e.g. or the like in a sealing groove.
  • components A and B are processed in a mixing ratio of 1: 1 with the aid of the two-component mixing and metering system, gear pumps being preferred.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Sealing Material Composition (AREA)

Claims (15)

  1. Procédé de préparation d'un élastomère de silicone, mou-élastique, alvéolaire ou non alvéolaire, en particulier à des fins d'étanchéité, ainsi que surtout pour des joints d'étanchéité pour carters et pour couvercles, des joints d'étanchéité destinés à la construction automobile et analogue, avec utilisation d'un système silicone à deux composants réticulant par addition, le composant A contenant :
    - un polymère de silicone avec au moins deux groupes vinyle pour chaque molécule,
    - un catalyseur au platine, ainsi que
    - le cas échéant d'autres additifs (individuellement ou en combinaison), tels qu'une charge, un pigment de coloration, un amélioreur d'adhérence, un agent de protection contre le vieillissement, des substances de renforcement,
    le composant B du réticulant contenant :
    - un siloxane d'hydrogène et, le cas échéant, d'autres additifs
    travaillé au moyen d'une installation de mélange et de dosage, travaillant sur deux composants et sans apport de chaleur pour obtenir la réaction, caractérisé en ce que sont ajoutées à au moins l'un des deux composants A et B, à titre de charge et d'agent d'étirement, des microbilles creuses élastiques se présentant sous la forme de billes creuses de polymère expansées, pourvues d'un enveloppement minéral non organique.
  2. Procédé selon la revendication 1, caractérisé en ce que les microbilles creuses citées sont ajoutées aux deux composants A et B avant leur mélange.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que sont utilisées des microbilles creuses dont la taille de grain ne dépasse pas 20U µm et de préférence est située dans la plage allant de 20 à 50 µm.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la proportion totale de charge constituée de microbilles creuses dans le système silicone constitué des composants A et B ne dépasse pas 30 % en poids par rapport à la proportion en poids du polymère de silicone utilisé, de préférence est située dans la plage allant de 2 à 20 % en poids du polymère de silicone.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on utilise des microbilles creuses en copolymère de polyacrylnitrile ou en copolymère de chlorure de polyvinylidène.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on utilise des microbilles creuses dont l'enveloppement minéral est constitué de carbonate de calcium (CaCO3).
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on ajoute pour la préparation d'une mousse de silicone, au composant A en plus de l'eau à titre d'agent gonflant, de préférence en une quantité maximale de 2 % en poids par rapport à la quantité globale de polymère de silicone.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que les composants A et B sont travaillés en un rapport de mélange de 1:1 dans l'installation de mélange et de dosage à deux composants, chacun des deux composants A et B contenant au moins deux groupes vinyle par molécule ainsi que, à titre de charge, les microbilles creuses citées, de préférence en des quantités égales.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que, pour la préparation de l'élastomère alvéolaire au silicone, on travaille avec les composants ci-après : Composant A : 100 g de polymère de silicone ayant au moins deux groupes vinyle par molécule 2 g d'eau 0,2 g de platine utilisé comme catalyseur 10 g de microbilles creuses expansées, enveloppées, par exemple, avec du CaCO3,
    Composant B : 100 g de polymère de silicone avec au moins deux groupes vinyle par molécule 10 g de siloxane d'hydrogène, par exemple du diméthylhydrogènesiloxane, 10 g de microbilles creuses expansées, enveloppées, par exemple, avec du CaCO3,
    les deux composants A et B précités étant travaillés à la température ambiante de, par exemple, 20 °C sur une installation de mélange et de dosage pour deux composants travaillant à basse pression.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que la transformation des composants A et B est effectuée, comme ceci est connu, sur une installation de mélange et de dosage à deux composants travaillant à basse pression, à une vitesse rotation de 3000 à 8000 tr/min. pour ce qui concerne l'organe de mélange entraîné de la tête de mélange, le canal de mélange axial ménagé dans la tête de mélange étant réglé de manière que l'intervalle existant entre la paroi de canal et l'organe de mélange tournant, disposé axialement dans le canal de mélange, soit de 0,5 à 3 mm.
  11. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que le système silicone constitué des composants A et B pour produire un moussage suivant la forme d'un moule est travaillé au moyen d'une installation de mélange et de dosage à deux composants travaillant sous haute pression.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que, pour préparer un élastomère de silicone non alvéolaire, le mélange de réaction constitué des composants A et B est travaillé sans eau comme agent gonflant et sans excès de siloxane d'hydrogène.
  13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce qu'on utilise comme catalyseur un catalyseur organique à base de platine qui contient, en se référant à 1000 g du polymère de silicone contenu dans la masse de réaction, une quantité comprise entre 300 et 3000 ppm, de préférence 300 à 900 ppm de platine.
  14. Procédé selon la revendication 13, caractérisé en ce qu'on utilise comme siloxane d'hydrogène un polysiloxane d'hydrogène ayant une teneur en SiH de 15 mmol/g.
  15. Procédé selon la revendication 13 ou 14, caractérisé en ce que l'élastomère de silicone, ou le produit constitué à partir de lui, est soumis à un recuit conduit sur une durée de 15 à 20 min. à une température de 120 °C à 150 °C.
EP95104158A 1995-03-22 1995-03-22 Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité Expired - Lifetime EP0733672B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59500604T DE59500604D1 (de) 1995-03-22 1995-03-22 Verfahren zum Herstellen eines geschäumten oder ungeschäumten weich-elastischen Silikonelastomers, insbesondere für Dichtungszwecke
EP95104158A EP0733672B1 (fr) 1995-03-22 1995-03-22 Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité
AT95104158T ATE157685T1 (de) 1995-03-22 1995-03-22 Verfahren zum herstellen eines geschäumten oder ungeschäumten weich-elastischen silikonelastomers, insbesondere für dichtungszwecke

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95104158A EP0733672B1 (fr) 1995-03-22 1995-03-22 Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité

Publications (2)

Publication Number Publication Date
EP0733672A1 EP0733672A1 (fr) 1996-09-25
EP0733672B1 true EP0733672B1 (fr) 1997-09-03

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EP95104158A Expired - Lifetime EP0733672B1 (fr) 1995-03-22 1995-03-22 Méthode pour préparer un mousse molle élastique silicone élastomérique, particulièrement pour joints d'étanchéité

Country Status (3)

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EP (1) EP0733672B1 (fr)
AT (1) ATE157685T1 (fr)
DE (1) DE59500604D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025224511A1 (fr) * 2024-04-25 2025-10-30 3M Innovative Properties Company Composites de mousse de silicone contenant des microsphères et leurs procédés de fabrication
WO2025259459A1 (fr) * 2024-06-14 2025-12-18 W.R. Meadows Compositions de formation de mousse de silicone et mousses de silicone fabriquées à partir de celles-ci

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2765884B1 (fr) 1997-07-09 2001-07-27 Rhodia Chimie Sa Composition silicone pour l'enduction de substrats en matiere souple, notamment textile
DE19745981B4 (de) * 1997-10-17 2012-09-27 Peter Maagh Reaktionsmischung mit mehreren Komponenten zur Abdichtung von Rohrverbindungen sowie deren Verwendung
AUPQ118399A0 (en) * 1999-06-24 1999-07-22 Selleys Pty Limited Novel composition container apparatus and process
AU5864100A (en) * 1999-07-28 2001-02-13 Akzo Nobel N.V. Expanded hollow micro sphere composite beads and method for their production
US7141738B2 (en) 2004-02-02 2006-11-28 3M Innovative Properties Company Re-enterable splice enclosure
US7214735B2 (en) * 2004-02-02 2007-05-08 3M Innovative Properties Company Microsphere-filled sealant materials
CN100381535C (zh) * 2006-02-28 2008-04-16 成都硅宝科技实业有限责任公司 防污染单组分室温硫化硅酮密封胶及其制造方法
CN116474750B (zh) * 2022-01-13 2025-03-04 中国石油化工股份有限公司 一种氧化铝载体及其成型方法和在加氢反应中的应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202362A (en) * 1991-09-09 1993-04-13 Intech Specialties Co., Inc. Syringeable ear plug molding putty composition
JP3274487B2 (ja) * 1992-01-30 2002-04-15 東レ・ダウコーニング・シリコーン株式会社 発泡性シリコーンゴム組成物およびシリコーンゴム発泡体の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025224511A1 (fr) * 2024-04-25 2025-10-30 3M Innovative Properties Company Composites de mousse de silicone contenant des microsphères et leurs procédés de fabrication
WO2025259459A1 (fr) * 2024-06-14 2025-12-18 W.R. Meadows Compositions de formation de mousse de silicone et mousses de silicone fabriquées à partir de celles-ci

Also Published As

Publication number Publication date
EP0733672A1 (fr) 1996-09-25
DE59500604D1 (de) 1997-10-09
ATE157685T1 (de) 1997-09-15

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